KR100547583B1 - Production of amides and/or acids from nitriles - Google Patents

Abstract

Introducing into the treatment zone a first reactant nitrile and a second reactant hydride compound (which may react with the nitrile to hydrate the nitrile to convert to a corresponding amide and / or to a corresponding acid). A method for producing amides and / or acids from nitriles. Nitrile is catalytically distilled in the treatment zone in the presence of a hydration compound and at least a portion of the nitrile is hydrated with the corresponding amide and / or forms a corresponding acid. Recover the amide and / or acid from the treatment zone.

Generation of Amides and / or Acids from Nitriles

Description

Production of Amides and / or Acids from Nitriles {PRODUCTION OF AMIDES AND / OR ACIDS FROM NITRILES}

The present invention relates to the production of amides and / or acids from nitriles. The present invention relates in particular to a process for the production of amides and / or acids from nitriles.

Summary of the Invention

According to the present invention there is provided a process for producing an amide and / or acid from a nitrile, wherein the nitrile is hydrated and / or hydrated as a first reactant and as a second reactant (to react with the nitrile to be converted to the corresponding amide) Introducing a hydrated compound, which can convert it into the corresponding acid, into the treatment zone; Nitrile is catalytically distilled in the treatment zone in the presence of a hydration compound to hydrate the minimum nitrile with the corresponding amide and / or to form the corresponding acid; Recovering the amide and / or acid from the treatment zone.

Catalytic distillation involves chemical reactions simultaneously with or in combination with distillation in a single treatment zone. The treatment zone is at least one reaction zone in which the reaction of hydration of nitrile with amides and / or acids in the presence of a catalyst takes place catalytically, and the distillation of the reaction product (s) and / or unreacted reactants from the reaction zone takes place. It will include at least one distillation zone adjacent to the reaction zone.

The reaction zone may comprise a packed bed of catalyst particles capable of catalyzing the conversion or hydration of nitriles to their corresponding amides. Any suitable hydration catalyst, typically copper or copper-based hydration catalyst, such as copper-chromium or copper oxide hydration catalyst may be used.

The first reactant may comprise unsaturated or aromatic nitriles such as acrylonitrile, methacrylonitrile, crotononitrile, allyl cyanide, or benzonitrile, which are corresponding unsaturated or aromatic amides without significant polymerization. And / or hydrated with acid. In practice, however, the first reactant may comprise saturated nitriles such as acetonitrile, propionitrile, butyronitrile, or isobutyronitrile.

Treatment zones will typically be provided in columns or towers, and catalyst beds are provided in tower zones. Distillation zones may be provided above and / or below the catalyst bed. Preferably, the distillation zone is provided above and below the catalyst bed. Suitable packing distillation media, such as Raschig rings, or distillation apparatus or equipment, are provided in the column, ie distillation zone (s), below and / or above the catalyst bed.

The process may include boiling liquid components in the reboiling zone operably connected to the lower end of the treatment zone to provide driving force for catalytic distillation. Some of the liquid component can be introduced into the treatment zone, for example, above or below the catalyst bed, if desired.

The liquid component can be assisted in the distillation of reactants and products in the treatment zone so as not to be involved in the hydration reaction, ie only provide a driving force for catalytic distillation. In this case, the second reactant may be fed to the treatment zone when the nitrile is fed to the treatment zone below the catalyst bed, for example, to the treatment zone at a location away from the point where the first reactant or nitrile is introduced into the treatment zone above the catalyst bed. . The second reactant should be able to hydrate the nitrile in the presence of a catalyst and conditions common to the treatment zone. In particular, the second reactant may be water.

The liquid component may be an organic compound such as an alcohol, an aromatic or paraffin.

However, the liquid component may be to participate in the hydration reaction. In particular it may be the same as the second reactant. That is, some of the second reactants are used for reboiling while being introduced into the treatment zone described above.

The higher boiling points of the first and second reactants can be introduced into the treatment zone above the catalyst bed, while the lower boiling ones are introduced below or above the catalyst bed. If the first reactant or nitrile is a higher boiling component, some of it will be introduced above the catalyst bed, while others boil in the boiling zone to provide the driving force for catalytic distillation.

The recovery of the amide can be carried out in the form of an overhead or distillate component at the top of the treatment zone of the reboiling zone or in the form of a high boiling component at the bottom of the treatment zone, depending on the relative boiling point of the first and second reactants.

The column can be the desired length and width and is typically 10m to 60m long. Typically, their diameters range from 25 mm to 110 mm on a test plant scale and at least 110 m for industrial scale operation. The catalyst layer can also be any desired length, for example 0.5-10 m. The pressure in the column can vary widely, for example 10 kPa (g) to 10000 kPa (g) and can be controlled by an inert gas such as nitrogen or argon. The pressure and reaction temperature inside the column will determine the product produced. Thus, if an amide corresponding to the nitrile supplied to the column is produced at a given column pressure and at a particular reaction temperature, rather increasing the column pressure and reaction temperature at which the reaction is carried out, a corresponding acid is produced, resulting in excess or excessive hydrolysis. Arises, forming the corresponding acid.

The figure is a diagram showing a simple flow diagram of a process according to the invention.

details

The invention will be described in more detail with reference to a drawing showing a simple flow diagram of a process according to the invention for producing amides and / or acids from nitriles, and with reference to non-limiting examples.

In the figure, reference numeral 10 generally denotes a process according to the invention for producing amides from nitriles.

Process 10 includes a catalytic distillation column 12. The size of column 12 may vary, but is typically about 10 m in length and 25 mm in diameter.

The reaction zone 14 is provided inside the column 12 such that the distillation zone 16 is provided above the zone 14, while another distillation zone 18 is provided below the reaction zone 14. Reaction zone 14 includes a support layer of a copper-based particulate hydration catalyst, such as a supported copper-chromium catalyst, a supported copper oxide catalyst or another similar hydration catalyst. Distillation zones 16 and 18 are packed with Raschig rings (not shown).

The water supply line 20 is connected to the column 12 above the layer 14, while the nitrile supply line 22 is connected to the column 12 just below the layer 14. However, nitrile feed line 22 may be connected to column 12 above layer 14.

Reboiler 24 is located at the bottom of column 12. Recovery line 26 is connected to reboiler 24 at the bottom of column 12, but return line 28 is connected back to column 12 at reboiler 24. The reboiler 24 is equipped with a heater 30, but the product recovery line 34 exits from the reboiler.

In use, sufficient water is introduced into the reboiler 24 to fill 30-80% of its capacity and to be heated. The pressure in column 12 is adjusted to the desired 0.1 to 100 bar by an inert gas such as nitrogen and argon. Water in reboiler 24 boils into column 12 until sufficient reflux is reached. At this stage, a feed stream of nitrile, for example acrylonitrile having a boiling point lower than water, is introduced into column 22 along feed line 22, typically at a rate of 0.001 to 50 kg / hour, and then Water is introduced along the feed line 20 at a feed rate, for example from 0.001 to 100 kg / hour. Typically, the nitrile used as feedstock is stabilized from polymerization with radical inhibitors such as hydroquinone or methylated hydroquinone prior to introduction to the column. Column 12 is maintained under reflux conditions and the amide product of nitrile is recovered in the form of a bottom stream along flow line 34 at a rate of 0.002 kg to 150 kg / hour with excess water.

According to process (10), the following non-limiting examples were carried out in the laboratory.

Example 1

The reduced form of copper-chromite catalyst pellets (650 g) supported in stainless steel wire sox (22) was packed in a 5 m section of a catalytic distillation column 12 having a size of 10 m height x 25 mm diameter. The top 1 meter of the column (zone 16) and the bottom 4 meters (zone 18) were filled with Raschig rings. The mineral-free water was introduced to the reboiler 24 to 30% of its capacity. Under a nitrogen atmosphere, water was boiled into the column under atmospheric pressure (85 kPa) until reflux (96 ° C.). Acrylonitrile containing 35 ppm of methylated hydroquinone (MeHQ) was introduced at a feed rate (flow line 22) just below the catalyst bed at a rate of 30 g / hour and water was added 84 g / hour above the catalyst zone. Supplied at a speed (flow line 20). After the introduction of acrylonitrile, the temperature inside the catalyst layer was dropped to the boiling point (64 ° C.) of the acrylonitrile-water azeotrope. The product solution (100% conversion and 100% selectivity) containing 35% by weight of acrylamide was recovered from the reboiler along the flow line 34 at a rate of 114 g / hour.

Example 2

An extrudate or pellet (350 g) of a reduced form of copper oxide or copper-chromite catalyst supported on stainless steel wire sox (10 pieces) and wrapped with demister wire (2.1 g in diameter and 35 mm in diameter) The upper section of the catalytic distillation column was packed. The bottom 600 mm of the column was filled with Raschig rings or distill packed. Air and mineral-free water were introduced into the reboiler to reach 30% of its capacity. Under a nitrogen atmosphere, water was boiled into the column under atmospheric pressure (85 kPa) until reflux (96 ° C.). The denitriated nitrile was introduced at a feed point just below the catalyst bed at a rate of 10-25 g / hour and water was fed to the column above the catalyst zone at the rate necessary to produce the desired product concentration. After introduction of the nitrile, the temperature inside the catalyst layer was lowered to the boiling point of the nitrile-water azeotrope. Product solutions (25-130 g / h) (> 90% conversion and selectivity) containing up to 50% by weight of amide were recovered from the reboiler.

Example 3

An extrudate (90 g) of a reduced form copper oxide catalyst supported on stainless steel wire sox (22 pieces) and wrapped with demister wire is packed in a 8.5 m section of a catalytic distillation column measuring 10 mx diameter 25 mm in height. I was. 10 mm Berl saddle was filled to the bottom 1.5 m of the column. Air and mineral-free water were introduced to the reboiler to 30% of its capacity. Under a nitrogen atmosphere of 200 kPa greater than atmospheric pressure, water was boiled into the column until reflux (135 ° C.). Deaired acrylonitrile (containing 35 ppm MeHQ) was introduced at the feed point just below the catalyst bed at a rate of 48-152 g / hour and water was fed at a rate such that the required product concentration was obtained in the column above the catalyst zone. did. After the introduction of acrylonitrile, the temperature inside the catalyst layer was reduced to the boiling point (about 104 ° C.) of the acrylonitrile-water azeotrope. Product solutions (> 98% conversion and selectivity) containing up to 50% by weight of acrylamide were recovered from the reboiler at a rate of 200-500 g / hour.

Example 4

In this example, the column apparatus and catalyst packing were the same as in Example 3, but the nitrogen pressure inside the column was raised to 400 kPa, which is larger than atmospheric pressure, to bring the reboiler temperature to 158 ° C. When acrylonitrile (180 g / h) is introduced above the catalyst zone, the temperature of the catalyst zone is reduced to 135-145 ° C. to give an aqueous solution of acrylic acid (about 75 g / h) and acrylamide (about 175 g / h). Generated.

Example 5

An extrudate of the reduced form copper oxide catalyst (13.5 kg) supported on a stainless steel wire sox and wrapped with demister wire was packed in a 7 m section of a catalytic distillation column 10 m high by 110 mm in diameter. The bottom of the column was filled with 10 mm Berl saddle at 2 m. Air and mineral-free water were introduced into the reboiler to 50% capacity. Under nitrogen pressure of 100 kPa above atmospheric pressure, water was boiled into the column until reflux (121 ° C.) was reached. Deaired acrylonitrile containing 35 ppm MeHQ was introduced at a feed rate above the catalyst bed at a rate of 0.5-2.5 g / hour and water was fed to the column above the catalyst zone at a rate to achieve the desired product concentration. After acrylonitrile introduction, the temperature inside the catalyst layer was reduced to the boiling point (about 89 ° C.) of the acrylonitrile-water azeotrope. The pH of the product solution was adjusted to 5.0-6.0 by adding 0.0125M sulfuric acid solution to the reboiler. Product solutions containing up to 50% by weight of acrylamide (> 98% conversion and selectivity) were recovered from the reboiler at a rate of 5-30 kg / hour.                 

It is known to produce amides from nitriles by hydration of nitriles in a batch, fixed or slurry bed reactor.

That is, three kinds of reactions are known:

a) homogeneous, mainly sulfuric acid, catalysis;

b) heterogeneous catalysis with copper or copper-based metal oxide mixtures as catalysts, for example copper oxide or chromium oxide;

c) A reaction that promotes hydration of the nitrile using a biocatalyst such as an enzyme.

These reactions are used for the production of amides, for example the production of acrylamide monomers from nitriles such as acrylonitrile. These monomers are again used in the production of water-soluble polymers and copolymers used as mining flocculants, paper making aids, thickening agents, surface coatings and enhanced oil recovery products.

Applicants know that in a sulfuric acid catalyzed batch process, very exothermic hydration of nitrile is involved in polymer formation unless the reaction temperature and reactant ratio are carefully controlled. To terminate the reaction, neutralizing the acid produces an effluent comprising sulfates primarily contaminated with acrylamide. This requires highly toxic acrylamide that must be crystallized from residual water and handled in powder form.

Applicants also find that polymerization and separation problems are prone to occur when processes involving heterogeneous catalysis use slurry-bed technology, but low concentrations in water, 7%, when a single fixed bed reactor, i. Only acrylamide is produced. Phase separation limits the amount of acrylonitrile that can be fed with water to the reactor.

In this case, the catalyst, unreacted acrylonitrile and water must be removed by filtration and / or distillation to reach the desired concentration of about 50%. Even without considering the uneconomical aspects associated with energy use (heat is removed in the reaction stage and added in the distillation stage), these processes are very capital intensive as many reactors and distillation towers require purification and concentration of the product. . The catalyst can in some cases be reduced and regenerated by hydrogen following oxidation, but catalyst life is also limited.

Applicants have surprisingly found that by applying catalytic distillation techniques to the hydration of amides, many disadvantages of known processes can be eliminated. The process of the present invention is a continuous process, which can significantly reduce the capital with little or no emissions produced (typically five reaction vessels for known processes compared to one reaction vessel). A further advantage is that the heat of reaction is partly used to heat the reactants, which shows lower energy requirements. Since catalytic distillation is essentially a distillation process, there is no difficulty in controlling the reaction temperature and thereby preventing or inhibiting unwanted polymerization. The required product concentration (50%) can be reached without additional separation process and catalyst life is improved. Since the product is constantly away from the heat source, little or no unwanted polymerization occurs. Thus, product aqueous solutions of the desired concentration (1% -60%) can be obtained directly from the reactor without further purification or concentration, but energy requirements are minimized. In the case of olefin nitriles, oligomerization / polymerization is not a problem if the pH is adjusted to 3 to 8 because the product is constantly away from the heat source.                 

Olefin amides such as acrylamide, methacrylamide, crotonamide, and 3-buteneamide, which may be prepared by the process of the present invention, may be used as monomers in the polymerization reaction. For example, nonionic and anionic polyacrylamides have been prepared from acrylamides produced by the process of the present invention. It is believed that the process of the present invention may produce acrylamide suitable for the production of cationic polyacrylamides.

Claims (15)

Introducing a nitrile as the first reactant and a hydrating compound into the treatment zone that can react with the nitrile to hydrate the nitrile and convert it to the corresponding amide; Catalytic distillation of the nitrile in the treatment zone in the presence of a hydration compound to hydrate some or all of the nitrile with the corresponding amide; Recovering the amide from the treatment zone. The process zone of claim 1, wherein the treatment zone comprises one or more reaction zones in which the hydration of nitrile to amides is catalytically in the presence of a catalyst, and reaction products or unreacted reactants adjacent to and from the reaction zone. At least one distillation zone in which distillation of the distillation takes place, and the reaction zone comprises a packing layer of copper or copper-based hydration catalyst particles. 3. The process of claim 2 wherein the first reactant comprises unsaturated or aromatic nitriles that are hydrated with corresponding unsaturated or aromatic amides. delete The process of claim 2 or 3, wherein the liquid component is boiled in a reboiling zone operably connected to the lower end of the treatment zone to provide a driving force for catalytic distillation, and a portion of the liquid component is optionally at the top of the catalyst bed or Introducing into the underlying treatment zone. 6. The method of claim 5, wherein the liquid component does not participate in the hydration reaction and provides only a driving force for catalytic distillation to assist in the distillation of the reactants and products in the treatment zone and at a location away from the point where the first reactant is introduced into the treatment zone. Supplying the second reactant to the treatment zone. Introducing a nitrile as a first reactant and a hydrating compound into the treatment zone that can react with the nitrile to hydrate the nitrile and convert it to the corresponding acid; Catalytic distillation of the nitrile in the treatment zone in the presence of a hydrating compound to convert some or all of the nitrile to the corresponding acid; Recovering acid from the treatment zone. 8. The treatment zone of claim 7, wherein the treatment zone comprises one or more reaction zones in which the hydration of nitrile to an acid occurs catalytically in the presence of a catalyst, and reaction products or unreacted reactants adjacent to and from the reaction zone. At least one distillation zone in which distillation of the distillation takes place, the reaction zone comprising a packing layer of copper or copper-based hydration catalyst particles. The method of claim 8, wherein the first reactant comprises unsaturated or aromatic nitriles that are hydrated with corresponding unsaturated or aromatic acids. 10. The process of claim 8 or 9, wherein the liquid component is boiled in a reboiling zone operably connected to the lower end of the treatment zone to provide propulsion for catalytic distillation and a portion of the liquid component is optionally at the top of the catalyst bed or Introducing into the underlying treatment zone. The process of claim 10 wherein the liquid component does not participate in the hydration reaction and provides only a driving force for catalytic distillation to assist in the distillation of the reactants and products in the treatment zone and at a location away from the point where the first reactant is introduced into the treatment zone. Supplying the second reactant to the treatment zone. delete delete delete delete

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